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Analytical Methods for Food Safety
by Mass Spectrometry
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Analytical Methods
for Food Safety by Mass
Spectrometry
Volume I Pesticides

Guo-Fang Pang
Academician, Chinese Academy of Engineering, Beijing, China
Chairman of the Academic Committee and a Chief Scientist of Beijing
Advanced Innovation Center for Food Nutrition and Human Health,
Beijing, China
Academic Press is an imprint of Elsevier
125 London Wall, London EC2Y 5AS, United Kingdom
525 B Street, Suite 1650, San Diego, CA 92101, United States
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom

Copyright © 2018 Chemical Industry Press.


Published by Elsevier Inc. under an exclusive license with Chemical Industry Press.

No part of this publication may be reproduced or transmitted in any form or by any means,
electronic or mechanical, including photocopying, recording, or any information storage and
retrieval system, without permission in writing from the publisher. Details on how to seek
permission, further information about the Publisher’s permissions policies and our
arrangements with organizations such as the Copyright Clearance Center and the Copyright
Licensing Agency, can be found at our website: www.elsevier.com/permissions.

This book and the individual contributions contained in it are protected under copyright by the
Publisher (other than as may be noted herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional practices,
or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in
evaluating and using any information, methods, compounds, or experiments described herein.
In using such information or methods they should be mindful of their own safety and the safety
of others, including parties for whom they have a professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors,
assume any liability for any injury and/or damage to persons or property as a matter of products
liability, negligence or otherwise, or from any use or operation of any methods, products,
instructions, or ideas contained in the material herein.
Library of Congress Cataloging-in-Publication Data
A catalog record for this book is available from the Library of Congress

British Library Cataloguing-in-Publication Data


A catalogue record for this book is available from the British Library

ISBN 978-0-12-814167-0

For information on all Academic Press publications visit our


website at https://www.elsevier.com/books-and-journals

Publisher: Andre Gerhard Wolff


Acquisition Editor: Patricia Osborn
Editorial Project Manager: Jaclyn Truesdell
Production Project Manager: Paul Prasad Chandramohan
Cover Designer: Greg Harris

Typeset by SPi Global, India


Contents

Main Researchers/Editors xiii


Preface xv
Brief Introduction xvii

1. Introduction 1
1.1 Insecticides 1
1.1.1 Organophosphate Insecticides 1
1.1.2 Carbamate Insecticides 2
1.1.3 Organochlorine Insecticides 2
1.1.4 Pyrethroid Insecticides 2
1.1.5 Neonicotinoid Insecticides 2
1.2 Herbicides 3
1.2.1 Phenolic Herbicides 3
1.2.2 Phenoxy Acid Herbicides 3
1.2.3 Benzoic Acid Herbicides 4
1.2.4 Diphenyl Ether Herbicides 4
1.2.5 Dinitroaniline Herbicides 4
1.2.6 Amide Herbicides 4
1.2.7 Carbamate Herbicides 5
1.2.8 Thiocarbamate Herbicides 5
1.2.9 Urea Herbicides 5
1.2.10 Sulfonylurea Herbicides 5
1.2.11 S-Triazine Herbicides 5
1.2.12 Quaternary Ammoniums Herbicides 6
1.2.13 Organophosphate Herbicides 6
1.2.14 Other Herbicides 6
1.3 Bactericides 6
1.3.1 Triazole Bactericides 7
1.3.2 Amide Bactericides 7
1.3.3 Pyridinamine Bactericides 7
1.3.4 Strobin Bactericides 7
1.3.5 Oxazo Bactericides 8
1.3.6 Pyrrole Bactericides 8
1.3.7 Amino Acid Bactericides 8
1.3.8 Derivants of Cinnamic Acid 8
1.3.9 Others 8

v
vi Contents

1.4 Pesticides Banned in the World 8


1.4.1 Pesticides Banned in China 8
1.4.2 Pesticides Banned in Japan 9
1.4.3 Pesticides Banned in European Union 9
2. Analytical Methods for 793 Pesticides and Related
Chemical Residues in Products of Plant Origin 11
2.1 Determination of 512 Pesticides and Related Chemical Residues
in Fruit Juice and Wine: LC-MS-MS Method (GB/T 23206-2008) 11
2.1.1 Scope 11
2.1.2 Principle 11
2.1.3 Reagents and Materials 11
2.1.4 Apparatus 21
2.1.5 Sample Pretreatment 21
2.1.6 Determination 22
2.1.7 Precision 24
Researchers 24
2.2 Determination of 500 Pesticides and Related Chemical Residues
in Fruits and Vegetables: GC-MS Method (GB/T 19648-2006) 25
2.2.1 Scope 25
2.2.2 Principle 25
2.2.3 Reagents and Materials 25
2.2.4 Apparatus 35
2.2.5 Sample Pretreatment 35
2.2.6 GC-MS Determination 36
2.2.7 Precision 37
Researchers 37
2.3 Determination of 450 Pesticides and Related Chemical Residues
in Fruits and Vegetables: LC-MS-MS Method
(GB/T 20769-2008) 37
2.3.1 Scope 37
2.3.2 Principle 45
2.3.3 Reagents and Materials 45
2.3.4 Apparatus 46
2.3.5 Sample Pretreatment 46
2.3.6 Determination 47
2.3.7 Precision 49
Researchers 50
2.4 Determination of 475 Pesticides and Related Chemical Residues
in Grains: GC-MS Method (GB/T 19649-2006) 50
2.4.1 Scope 50
2.4.2 Principle 50
2.4.3 Reagents and Materials 50
2.4.4 Apparatus 59
2.4.5 Sample Pretreatment 59
2.4.6 GC-MS Method Determination 60
2.4.7 Precision 61
Researchers 61
Contents vii

2.5 Determination of 486 Pesticides and Related Chemical Residues


in Grains: LC-MS-MS Method (GB/T 20770-2008) 61
2.5.1 Scope 61
2.5.2 Principle 69
2.5.3 Reagents and Materials 69
2.5.4 Apparatus 71
2.5.5 Sample Pretreatment 71
2.5.6 Determination 72
2.5.7 Precision 73
Researchers 73
2.6 Determination of 519 Pesticides and Related Chemical
Residues in Tea Leaves: GC-MS Method (GB/T 23204-2008) 74
2.6.1 Scope 74
2.6.2 Determination of 490 Pesticides and Related Chemical
Residues in Tea: GC-MS Method 74
2.6.3 Determination of 29 Acidic Herbicides in Tea:
GC-MS Method 85
Researchers 91
2.7 Determination of 448 Pesticides and Related Chemical
Residues in Tea Leaves: LC-MS-MS Method (GB/T23205-2008) 92
2.7.1 Scope 92
2.7.2 Principle 92
2.7.3 Reagents and Materials 92
2.7.4 Apparatus 101
2.7.5 Sample Pretreatment 101
2.7.6 Determination 102
2.7.7 Precision 103
Researchers 103
2.8 Determination of 488 Pesticides and Related Chemical
Residues in Mulberry Twig, Honeysuckle, Barbary Wolfberry
Fruit, and Lotus Leaf: GC-MS Method (GB/T 23200-2008) 103
2.8.1 Scope 103
2.8.2 Principle 104
2.8.3 Reagents and Materials 104
2.8.4 Apparatus 113
2.8.5 Sample Pretreatment 113
2.8.6 Determination 114
2.8.7 Precision 115
Researchers 115
2.9 Determination of 413 Pesticides and Related Chemical
Residues in Mulberry Twig, Honeysuckle, Barbary Wolfberry
Fruit, and Lotus Leaf: LC-MS-MS Method (GB/T 23201-2008) 115
2.9.1 Scope 115
2.9.2 Principle 115
2.9.3 Reagents and Materials 116
2.9.4 Apparatus 123
2.9.5 Sample Pretreatment 123
2.9.6 Determination 124
2.9.7 Precision 126
Researchers 126
viii Contents

2.10 Determination of 503 Pesticides and Related Chemical


Residues in Mushrooms: GC-MS Method (GB/T 23216-2008) 126
2.10.1 Scope 126
2.10.2 Principle 126
2.10.3 Reagents and Materials 127
2.10.4 Apparatus 136
2.10.5 Sample Pretreatment 136
2.10.6 Determination 137
2.10.7 Precision 138
Researchers 138
2.11 Determination of 440 Pesticides and Related Chemical
Residues in Edible Fungus: LC-MS-MS Method
(GB/T 23202-2008) 138
2.11.1 Scope 138
2.11.2 Principle 138
2.11.3 Reagents and Materials 146
2.11.4 Apparatus 147
2.11.5 Sample Pretreatment 147
2.11.6 Determination 148
2.11.7 Precision 149
Researchers 149

3. Analytical Methods for 790 Pesticides and Related


Chemical Residues in Products of Animal Origin 151
3.1 Determination of 511 Pesticides and Related Chemical
Residues in Milk and Milk Powder: GC-MS Method
(GB/T 23210-2008) 151
3.1.1 Scope 151
3.1.2 Principle 151
3.1.3 Reagents and Materials 151
3.1.4 Apparatus 162
3.1.5 Sample Pretreatment 162
3.1.6 Determination 163
3.1.7 Precision 164
Researchers 164
3.2 Determination of 493 Pesticides and Related Chemical
Residues in Milk and Milk Powder: LC-MS-MS Method
(GB/T 23211-2008) 165
3.2.1 Scope 165
3.2.2 Principle 165
3.2.3 Reagents and Materials 165
3.2.4 Apparatus 175
3.2.5 Sample Pretreatment 175
3.2.6 Determination 176
3.2.7 Precision 178
Researchers 178
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Contents ix

3.3 Determination of 485 Pesticides and Related Chemical


Residues in Fugu, Eel, and Prawn: GC-MS Method
(GB/T 23207-2008) 179
3.3.1 Scope 179
3.3.2 Principle 187
3.3.3 Reagents and Materials 187
3.3.4 Apparatus 188
3.3.5 Sample Pretreatment 189
3.3.6 Determination 190
3.3.7 Precision 191
Researchers 191
3.4 Determination of 450 Pesticides and Related Chemical
Residues in Fugu, Eel, and Prawn: LC-MS-MS Method
(GB/T 23208-2008) 192
3.4.1 Scope 192
3.4.2 Principle 200
3.4.3 Reagents and Materials 200
3.4.4 Apparatus 201
3.4.5 Sample Pretreatment 201
3.4.6 Determination 203
3.4.7 Precision 204
Researchers 204
3.5 Determination of 497 Pesticides and Related Chemical
Residues in Honey, Fruit Juice, and Wine: GC-MS Method
(GB/T 19426-2006) 204
3.5.1 Scope 204
3.5.2 Principle 204
3.5.3 Reagents and Materials 213
3.5.4 Apparatus 214
3.5.5 Sample Pretreatment 214
3.5.6 Determination 215
3.5.7 Precision 216
Researchers 217
3.6 Determination of 486 Pesticides and Related Chemical
Residues in Honey: LC-MS-MS Method (GB/T 20771-2008) 217
3.6.1 Scope 217
3.6.2 Principle 217
3.6.3 Reagents and Materials 217
3.6.4 Apparatus 227
3.6.5 Sample Pretreatment 227
3.6.6 Determination 228
3.6.7 Precision 232
Researchers 232
3.7 Determination of 478 Pesticides and Related Chemical
Residues in Animal Muscles: GC-MS Method
(GB/T 19650-2006) 232
3.7.1 Scope 232
3.7.2 Principle 232
x Contents

3.7.3 Reagents and Materials 232


3.7.4 Apparatus 242
3.7.5 Sample Pretreatment 242
3.7.6 Determination 243
3.7.7 Precision 244
Researchers 244
3.8 Determination of 461 Pesticides and Related Chemical
Residues in Animal Muscles: LC-MS-MS Method
(GB/T 20772-2008) 245
3.8.1 Scope 245
3.8.2 Principle 253
3.8.3 Reagents and Materials 253
3.8.4 Apparatus 254
3.8.5 Sample Pretreatment 254
3.8.6 Determination 256
3.8.7 Precision 257
Researchers 257

4. Determination of 450 Pesticides and Related


Chemical Residues in Drinking Water: LC-MS-MS
Method (GB/T 23214-2008) 259
4.1 Scope 259
4.2 Principle 259
4.3 Reagents and Materials 259
4.4 Apparatus 268
4.5 Sample Pretreatment 269
4.5.1 Preparation of Test Sample 269
4.5.2 Extraction 269
4.5.3 Clean-up 269
4.6 Determination 269
4.6.1 LC-MS-MS Operating Condition 269
4.6.2 Qualitative Determination 271
4.6.3 Quantitative Determination 271
4.7 Precision 272
Researchers 272

5. Basic Research on Chromatography-Mass Spectroscopy


Characteristic Parameters of Pesticide and Chemical
Pollutants 273
5.1 Mass Spectrometry Data of 1200 Pesticides and Chemical
Pollutants Determined by GC-MS, GC-MS-MS, and LC-MS-MS 277
5.1.1 Retention Times, Quantifier and Qualifier Ions of
567 Pesticides and Chemical Pollutants Determined
by GC-MS 277
5.1.2 Monitoring of Selected Ions for 567 Pesticides
and Chemical Pollutants Determined by GC-MS 311
Contents xi

5.1.3 Retention Time, Quantifier and Qualifier Ions, and


Collision Energies of 454 Pesticides and Chemical
Pollutants Determined by GC-MS-MS 321
5.1.4 Monitoring of Selected Ions for 454 Pesticides
and Chemical Pollutants Determined
by GC-MS-MS 349
5.1.5 Retention Time, Quantifier and Qualifier Ions,
and Collision Energies of 284 Environmental Pollutants
by GC-MS-MS 356
5.1.6 Retention Times, Selective Ions, and Relative Abundances
of Endosulfans Determined by GC-NCI-MS 374
5.1.7 Retention Times, Quantifying and Qualifying Ions,
Declustering Potentials, and Collision Energies of 9
Environmental Pollutants Determined by LC-MS-MS 375
5.1.8 Retention Times, Quantifying and Qualifying Ions,
Fragmentor, and Collision Energies of 569 Pesticides
and Chemical Pollutants Determined by LC-MS-MS 376
5.1.9 Accurate Masses, Retention Times, Parent Ions,
and Collision Energies of 492 Pesticides and Chemical
Pollutants Determined by LC-TOF-MS 410
5.2 Linear Equation Parameters of 1200 Pesticides and
Chemical Pollutants Determined by GC-MS, GC-MS-MS,
and LC-MS-MS 457
5.2.1 Linear Equations, Linear Ranges, and Correlation
Coefficients of 567 Pesticides and Chemical Pollutants
Determined by GC-MS 457
5.2.2 Linear Equations, Linear Ranges, and Correlation
Coefficients of 466 Pesticides and Chemical Pollutants
Determined by GC-MS-MS 491
5.2.3 Linear Equations, Linear Ranges, and Correlation
Coefficients of 284 Environmental Pollutants Determined
by GC-MS-MS 519
5.2.4 Linear Equations, Linear Ranges, and Correlation
Coefficients of Endosulfans Determined
by GC-MS(NCI) 536
5.2.5 Linear Equations, Linear Ranges, and Correlation
Coefficients of 9 Environmental Pollutants Determined
by LC-MS-MS 537
5.2.6 Linear Equations, Linear Ranges, and Correlation
Coefficients of 569 Pesticides and Chemical Pollutants
Determined by LC-MS-MS 538
5.3 GPC Analytical Parameters of Pesticides and Chemical
Pollutants 572
5.3.1 GPC Analytical Parameters of 744 Pesticides
and Chemical Pollutants 572
5.3.2 GPC Analytical Parameters of 107 Pesticides
and Chemical Pollutants 599
xii Contents

Appendix A: Index of 1039 Pesticides and Chemical Pollutants Determined


by GC-MS, GC-MS-MS and LC-MS-MS 603
Appendix B: Solvent Selected and Concentration of Mixed Standard
Solution of Pesticides and Chemical Pollutants 661
Appendix C: Physicochemical Properties of 900 Pesticides
and Chemical Pollutants 707
Appendix D: MRM Chromatograms of 493 Pesticides
and Related Chemicals 791

Index 857
Main Researchers/Editors

Guo-Fang Pang
Qiao-Ying Chang
Chun-Lin Fan
Yan-Zhong Cao
Yong-Ming Liu

xiii
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Preface

Today more and more requirements and restrictions are being placed on the res-
idues of pesticides and veterinary drugs in edible animal and plant-derived agri-
cultural products all over the world, and more and more kinds of pesticides must
be controlled. Meanwhile, the index of maximum residue limit (MRL) for pes-
ticides is getting lower, so the barriers to international trade of edible agricul-
tural products are becoming higher.
The research team of Guo-Fang Pang took the lead in research focusing on
the strategic development of food safety. They met the challenge, and a series of
low-cost and highly efficient detection methods have been established.
In the field of pesticide residues determination, the authors conducted a sys-
tematic study of the detection of multiclasses and multitypes of pesticide res-
idues in different edible agricultural products, and 20 high-throughput
sample preparation and analytical methods were developed for simultaneous
extraction, separation, enrichment and determination of 400–500 pesticide
residues with a once-for-all sample preparation. These methods are applicable
to the simultaneous determination of multipesticide residues in animal and
plant-derived agricultural products, such as fruit juices, vegetable juices, fruit
wines, fruits, vegetables, cereals, tea, Chinese medicinal herbs (such as ramulus
mori, honeysuckle, Chinese wolfberry, and lotus leaf), edible fungi (such as
mushrooms), honey, milk, milk powder, aquatic products (such as globefish,
eel, and prawn), animal muscle tissues, and drinking water. A high-selectivity,
high-sensitivity, high-resolution, and high-throughput analysis methodology
for the detection of more than 1000 pesticide residues has been established.
These methods are considered to be the international leaders in the type and
quantity of pesticides that can be detected simultaneously.
In veterinary drug residue detection, the authors have established 65 high-
selectivity, high-sensitivity veterinary drug residue detection methods for the
determination of 20 types of nearly 200 commonly used veterinary drugs that
may be residual in edible animal-derived agricultural products, and the methods
are applicable to samples with complicated bases, such as edible animal tissue
(such as muscle, liver, kidney, and fat), milk, milk powder, bee products (such
as honey, royal jelly, and its lyophilized powder), aquatic products (such as
globefish, eel, and prawn), and animal urine.
This book is a systemic summary of the research of Guo-Fang Pang’s
team on the theory and applied practice of detection technology of pesticide
residues over the past 20 years. The innovative research achievements at an

xv
xvi Preface

internationally advanced level in this field are fully demonstrated in this work.
In addition, the progress of food safety detection technology has been promoted.
This is mainly reflected in the following aspects:
1. High-throughput sample pretreatment technology: A series of technical
problems such as the extraction of pesticide and veterinary drug residues
at the level of micrograms per kilogram in various complex matrix samples
and the effective purification of the CO-extracted disrupting chemicals have
been overcome, and high-throughput sample preparation and purification
technology at an international leading level has been developed. Implemen-
tation of the detection of 400–500 pesticide residues simultaneously using
one sample preparation has been achieved.
2. The most comprehensive database available of pesticide mass spectrometry
has been constructed: gas chromatography-(tandem) mass spectrometry and
liquid chromatography-(tandem) mass spectrometry characteristics of 1000
commonly used pesticides worldwide were systematically studied and a data-
base with tens of thousands of mass spectra has been constructed. The database
can provide a qualitative and quantitative basis and has laid the foundation for
research and development of high-throughput detection technology.
3. A new technique of group detection by time intervals using chromatography
and mass spectrometry is proposed: pesticides with similar chemical proper-
ties and retention times are divided into several groups in turn; thus, the selec-
tivity of the method can be enhanced. Each group of pesticides is detected
according to the peak order and the time intervals, so the selectivity of the sen-
sitivity of the methods can be improved and the monitoring range expanded.
Furthermore, academician Pang’s team also cooperated fully with units from the
quality inspection system of China, institutions of higher learning, and scientific
research institutes for collaborative verification of the reliability and applicability
of the methods, thus leading to the formation of Chinese national standards (GB/T
series standards). These methods have been widely used in the detection of pesti-
cide and veterinary drug residues in edible animal and plant-derived agricultural
products and they have made a great contribution to the guarantee of food safety
in China. We believe these methods will provide a useful reference value for edible
animal and plant-derived agricultural product safety detection all over the world.
The book is suitable for scientific researchers in the residues testing areas
and technicians working in agricultural products testing and inspection, as well
as teachers and scholars of higher learning institutions as their reading material
or reference literature.

October 10, 2017


Brief Introduction
Food safety is a major security issue necessary to ensure the sound development
of human society. The widespread use of pesticides, veterinary drugs, and other
agricultural chemicals have contributed to widespread contamination in
agricultural products. The long-term consumption of food with high residues
of pesticides and veterinary drugs will cause both acute and chronic toxicity
in humans and induce resistant strains, thus resulting in allergies, cancer,
mutation, and teratogenicity. In order to ensure human health and food safety,
countries all over the world have issued strict food safety and hygiene standards.
The People’s Republic of China (PRC) has implemented strict monitoring of
pesticide and veterinary drug residues, such as maximum residue limits for
veterinary drugs in food of animal origin (Announcement No. 235 of the
Ministry of Agriculture of the People’s Republic of China) and national food
safety standards: Maximum residue limits for pesticides in food (GB 2763-
2016). The commonly used pesticides and veterinary drugs approved in China
and the main agricultural products of urban residents’ daily consumption are
almost all covered.
The book is a systematic summary of the high-throughput chromatography-
mass spectrometry technique for the analysis of multipesticides, veterinary
drugs, and other agricultural chemical residues in agriculture products of plant
and animal origin. Its technical characteristics are mainly embodied in the
simultaneous determination of hundreds of compounds, as well as low cost
and high efficiency.
This book is divided into two volumes. In Volume 1, pesticides and related
chemicals are selected as the main research object, while gas chromatography-
mass spectrometry (GC-MS), gas chromatography-tandem mass spectrometry
(GC-MS-MS), and liquid chromatography-tandem mass spectrometry (LC-MS-
MS) are concerned. This volume includes more than 20 analytical methods for
the high-throughput analysis of multipesticide residues, and more than 1000
pesticides and related chemicals in more than 10 kinds of agricultural products
and drinking water can be detected, and 400–500 kinds of pesticide residues can
be detected simultaneously with the pretreatment undertaken just once. The
methods for the analysis of 793 pesticides and related chemical residues in
foods of plant origin applicable to fruit juices, vegetable juices, fruit wines,
fruits, vegetables, cereals, tea, Chinese medicinal herbs (ramulus mori, honey-
suckle, Chinese wolfberry, and lotus leaf), and edible fungi (mushroom) are
introduced in Part 1; the methods for the analysis of 790 pesticides and related
chemical residues in foods of animal origin applicable to honey, milk, milk

xvii
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xviii Brief Introduction

powder, aquatic products (globefish, eel, and prawn), and animal muscle tissues
are presented in Part 2; while the methods for the analysis of 450 pesticides and
related chemical residues in drinking water are introduced in Part 3. Further-
more, the three major parameter databases adopted in the analysis of more
than 1000 pesticides and related chemicals are also included in this volume:
①chromatography-mass spectrometry characteristic parameters include reten-
tion time, quantitative and qualitative ions, fragment voltage and collision
energy, etc.; ②performance parameters of the methods include linear equation,
linear range and correlation coefficient, etc.; and ③gel permeation chromatog-
raphy (GPC) purification analysis parameters.
In Volume 2, the methods for the analysis of 20 species (nearly 200 kinds) of
veterinary drug residues in edible animal tissues (muscle, liver, kidney, and fat),
dairies (milk and milk powder), bee products (honey, royal jelly, and its lyoph-
ilized powder), aquatic products (globefish, eel, and roasted eel) and animal
urine are selected as main subjects of study. The 65 analytical methods for
the analysis of multiveterinary drug residues are described in different chapters
by category (sulfonamides, β-adrenergic agonists, aminoglycosides, chloram-
phenicols, β-lactams, macrolides, nitrofurans, anabolic steroids, nonsteroidal
anabolic steroids, glucocorticoids, fluoroquinolones, tetracyclines, sedatives,
pyrazolones, quinoxalines, nitromidazoles, benzimidazoles, levamisole, thio-
urea pyrimidines, and polyethers), and 90% of the methods are LC-MS-MS.
Meanwhile the physical and chemical properties, efficacy, side effects, and
maximum allowable residual limit of all the compounds are also provided.
In short, this book is the summary of the work of the author team who, for
more than 20 years, engaged in the research and practice of detection technol-
ogy of pesticides and veterinary drug residues. These methods for the analysis
of pesticides and veterinary drugs are innovative research results based on the
international frontier of pesticides and veterinary drug residue analysis, and the
analytical techniques adopted are new technologies widely concerned in the
field of residue analysis in the world today. The performance indexes of the
methods can meet the requirements of the Codex Alimentarius Commission
and the world’s major developed countries; meanwhile the methods are in
conformity with the developing trend of international residue analysis and they
are advanced in the world. In addition, the methods established in this book have
become the current effective national standard methods in China and they can
be used as the detection basis of relevant testing institutions and the law basis of
the relevant government departments. Nevertheless, due to the limitations of the
level, there may be unavoidable errors. We would kindly ask the users of this
publication to provide feedback to the authors so that subsequent editions may
be improved upon.

Guo-Fang Pang
Chapter 1

Introduction
Pesticides are chemical and biological products used to control, destroy, repel, or
attack organisms such as pests, mites, eelworms, pathogens, weeds, and mice.
According to their functions, pesticides can be categorized as insecticides,
fungicides, nematocides, molluscicides, bacteriocides, attractants, fumigants,
rodenticides, defoliants, desiccants, insect growth and plant growth regulators,
etc. Alternatively, based on the functional groups of their molecular structures, pes-
ticides can be categorized as inorganic pesticides, organochlorine insecticides,
organophosphate pesticides, carbamate pesticides, triazine herbicides, etc.
Pesticides are important materials in modern agriculture production because
they play a key role in preventing and controlling infectious diseases and
enhancing production yields at harvest. However, the long-term use of pesti-
cides has also resulted in significant contamination of the soil, the air we
breathe, and the environment.

1.1 INSECTICIDES
Insecticides are used in agriculture, medicine, industry, and our homes against
insects at all developmental stages. Many insecticides are also used against eggs
and larvae of insects, such as omethoate, monocrotophos and fenpropathrin, etc.
Insecticides fall into two types: inorganic and organic. Inorganic insecticides
are compounds containing arsenic, copper, lead, or mercury. They are highly
persistent in terrestrial environments, and are slowly dispersed through leaching
and erosion by wind and water. Inorganic insecticides are used much less now
than previously, having been widely replaced by synthetic organic insecticides.
Organic insecticides can be categorized as natural and synthetic. Natural insec-
ticides include botanical and biological insecticides. There are many types of
synthetic organic insecticides, including organophosphates, carbamates, organ-
ochlorines, and pyrethroids.

1.1.1 Organophosphate Insecticides


The function of organophosphate insecticides is to inhibit the activity of
cholinesterase of nerve tissue in insects and eventually to kill them. Usage of
organophosphate insecticides has a long history. Today, many organophos-
phate insecticides, including parathion, dichlorvos, fenitrothion, fenthion,

Analytical Methods for Food Safety by Mass Spectrometry. https://doi.org/10.1016/B978-0-12-814167-0.00001-6


Copyright © 2018 Chemical Industry Press. 1
Published by Elsevier Inc. under an exclusive license with Chemical Industry Press.
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Yea, or sitting a-drinking
In some snug corner with “fill the can, fill.”
Fy, niece, in the country Dickon or Will
Know well how to go with the lasses amids the rye,
And when at even their sports they ply,
Hath not Gill won a pretty forfeit from Jack?
Fy, niece, ere now ye have got a green gown to your back.
At home, I doubt not, many brisk lads there be.

MARY
Why say ye so, aunt?

AUNT
Ay, mistress hypocrisy!
Though the truth on’t cannot be told, I’ll be bound,
Ye have tripped it lightly many a round
Where the piper got not five groats for his noise.
Let ’em go to it never so with the boys,
’Tis all virgin, ay, till girdles be let out.

MARY
That I should be so shent and shamed, without
All guilt, is more than heart can bear.

AUNT
And I have spoke with them too who would swear
They saw you and your own eme in such guise
That it cannot be told of in no seemly wise.
All our kin ye bring to scandal and shame.
Tush, vile progeny, ye be too much to blame,
Out of my sight! Ye do mine eyes no good!

MARY
Lord God, what woe is mine in mood!
How doth the blood forsake my body utterly.
So vile reproach, such words of ignomy,
To hear and suffer, all unmerited!
Now, aunt, tell me if ye will make me a bed
For this one night?

AUNT
Ye were me liefer lie,
As deep as this roof-tree is high,
In the Meuse as bait for all its fish.
Be gone, ere you repent your wish.
I tremble like a leaf for teen.

MARY
Ye do me wrong, aunt.

AUNT
Stay, this cursed quean
With vexing me will not be done or quit.
Would ye have those fine braids tousled a bit?—
Yea, she rouses the maggot in my head.
I could bring the devil himself to bed
And bind him to the pillow like a doting wight.
I be grown so awry with spite,
I know not if I stand on head or feet.
To them withall that I today meet
I shall make answer, wherefor wrathful I am,
Even the same answer as the devil giveth his dam.

MARY
Ah, wretch! now be ye fallen on sorry days.
I stand here as one in a maze,
And of myself I know not the what or the how;
Meseems, I should have run frantic from the town erenow,
Mindful nor of knaves nor of thieves.
Under the trees I will make me a bed of leaves.
I reck not whom I meet, be it fremd or kin,
Though the devil came in his own proper skin.
To ask no questions thinketh me best.
Under this hedge I will sit me down to rest,
Yielding myself, for ill or well,
To god or all the fiends of hell.

¶ How Mary took leave of her aunt and departed out of


Nimmegen.

Thus is the young maiden, Mary, departed from her aunt and
piteously weeping in sore distress hath betaken her out of the town
Nimmegen in the dark of evening, until she is come to a great thick
hedge, beneath the which she sat her down in sorrowful mood,
weeping and wailing, and oft commending herself to the devil, and to
herself sorrowfully saying:

Weeping and wailing and mine hands wringing,


Calling myself maledight,
Be all my solace and none other thing,
By cause mine aunt hath done me despite.
Is it wrong that I should be in spite
That causeless she blamëd me at erst?
Nay! Such anger doth on me alight
And waxeth in my heart aright,
That I sit here in wrathful plight
And ever hold myself accurst.

Help, what temptations on me throng!


Shall I yet do some violence?
Ah, youth, canst thou bear up so long?
Can reason offer no defence?
How should I stomach such offence
All guiltless? Whosoe’er he be,
None living hath patience.
Wanhope doth drive me from my sense.
Help me lament mine innocence,
God or the Devil, ’tis all one to me.
¶ The Devil, who always spreadeth his nets and snares wherein to
catch souls ripe unto damnation, on hearing these words said with
himself as follows:

Ah! I’m the richer by one more soul!


Ye see me disguised and, on the whole,
Quite the sort of gentleman God approves,
And, except for my one eye, just as behoves;
The other perchance was cast out by a spell.
It’s not in our power, we devils of hell,
To incarnate ourselves, as ye are aware,
Without some little defect here or there,
Be it in the head or the hands or the feet.
Now as I may I will make my voice sweet,
And speak with such modest and winsome cheer
As to do none offense to my sweet lemman here.
With the women ’tis doucely at first that gets on.
Fair child, why sit ye here sorrow-begone?
Hath some one misdone you, sans reason or right,
As a good honest fellow would gladly requite?
The picture of innocence, child, ye resemble,
Wherefore I would comfort you.

MARY
Help, God, how I tremble!
How stands it with me? I know not aright
Since first this good man came on my sight.
Help, how all faintly throbbeth my heart!

THE DEVIL
Fair child, fear ye no grief nor smart.
I will do you neither harm nor let,
But I make avouch if your course ye will set
By my avise, and go with me by all means,
I will make you ere long a queen among queens.
...
MARY
... Friend,
I sit now all at my wits’ end,
This my machine so wrought to hurt
By shameful words, the which without desert
I needs must bear: slut, harlot, whore,
That to the Fiend I’d liefly give me o’er
As to God, for I be half from my wit.

THE DEVIL
By Lucifer, ’tis purchase, all of it!
She hath drunk up her wrath at one
And sits in wanhope like a stone.
Hope bids me shed no tears today:
I shall not fail.—Fair child, I pray
That we in friendship may agree.

MARY
Who are ye, friend?

THE DEVIL
A master of much subtlety,
Who never comes short in aught he essays.

MARY
It skills not with whom I go my ways,
As well with the worst as with the best.

THE DEVIL
If to mewards your love were dress’d
I would teach you in all their parts
Music, rhetoric, all the seven arts,
Logic, grammar, geometry,
Arithmetic and alchemy,
All the which be worthy of heed;
No woman on earth in learning shall speed
As ye shall do.

MARY
Ye should have potent gramerye.
Who may ye be?

THE DEVIL
Why, what care ye?
To ask me that ’twere wiser not.
In truth, I am not the best of my lot.
But none could love you as well as I.

MARY
How hight ye, friend?

THE DEVIL
Moonen with the single eye,
Whom all good fellows know right well.

MARY
Ye be the devil out of hell!

THE DEVIL
At least your humble servant and true friend.

MARY
Strange, but ye do not me offend.
Though Lucifer self were come from hell,
I stand in case to greet him well.
I be wholly quit of fear.

THE DEVIL
So this is the short and long, my dear:
If you will do after my rate,
All that your fancy may dictate
I’ll teach you, as at erst I told.
Of goods, of jewels, or of gold
Ye shall never more have need.

MARY
’Tis well said; but by your rede,
Ere we be given each to each,
The seven arts ye shall me teach,
For in such learning I would speed.
Ye will me teach them?

THE DEVIL
Faith, in deed.
All seemly lore I will impart.

MARY
Nigromancy is a merry art.
Mine eme therein hath a pretty wit.
He hath a book and wonders works with it,
Nor never fails, he is so sly.
He can through the needle’s eye
Send the devil a-creeping willy-nilly.
That trick I fain would learn.

THE DEVIL
Ah, silly,
My knowledge is wholly at your device.
But I never studied, to be precise,
Nigromancy in all its parts.
It is quite the hardest of all the arts,
And for a novice perilous as well.
Suppose there’s wanting in your spell
A word or letter wherewithal
Ye would make the spirit that ye call
Your wishes duly to obey,
The fiend would break your neck straightway.
My dear, be sure there’s mischief in it.

MARY
Well, in that case I’ll not begin it.
I would not meet death in such a kind.

THE DEVIL
Ha, ha! I’ve put that out of her mind,
What would she be wanting to learn such a thing?
An she did, it would not be long ere she’d bring
On all us poor spirits the worst of our fears,
At her own sweet will set all hell by the ears,
And force even me in some dreadful tight squeak.
I teach her nigromancy? Not this week!
It is something at all costs she must not consider of.—
Now hearken to what I shall teach you, my love.
If nigromancy ye will wholly let be.

MARY
What will ye teach me?

THE DEVIL
Ah, let us see.
I will make you master of every tongue,
So that far and wide your fame shall be rung.
In the knowledge of tongues much virtue abides,
And the seven liberal arts there besides.
Ye shall be exalted of all and each.

MARY
My sorrow wanes at your fair speech.
Do that, and wholly at your will
I hold me.

THE DEVIL
One little matter still;
But grant my prayer, and well will you betide.

MARY
What is your prayer?

THE DEVIL
To lay your name aside.
And give yourself another therefor.
Mary’s a name I never learned to care for.
Along of one Mary I and my fellows into such mischief fell
That ’tis a name we like but indifferent well.
Were ye called Lisbeth or Lina or Gretchen, my dear,
It would get you more, I’ll be sworn, in a year
Than ever ye had of kin or kith.

MARY
Alas, wherefore do ye take ill therewith?
’Tis ever the sweetest and noblest name
That the tongue of man can fashion or frame.
Why should ye thereagainst make war?
I may not change, for worlds and more,
A name which nought could make more sweet.

THE DEVIL
Tut, tut! It’s all about one’s feet
Again, but if she will thereto consent!—
Would we, my dear, to our content
Go wandering, ye must change that name,
Or here we part. Yet more I claim
Of you. A promise is a debt.

MARY
What must it be?

THE DEVIL
Not to forget,
Come weal, come woe, I cannot bear
To have you cross yourself.

MARY
I grant it well and fair.
On crossing I set but little store.
But my name I can ill brook to give o’er.
For Maria, whence I have it, is my hope and trust,
And when in sorrow I am thrust
I cry on her to intercede.
Daily thus I bid my bede
Even as a child I learned it of yore.
Praised be Mary evermore!
While I have life I will ne’er have done,
Though wild and wanton I may run,
With praising her, nor at all forget.

THE DEVIL
Well, since your will be wholly set
Upon this name, I will somewhat abate:
Of all the letters keep at any rate
The first and drop the other three;
That is the M, and Emma shall ye be,
As in your countryside be many a maid and dame.

MARY
Well, since I may not have my proper name
I were indeed to blame, if we parted for a letter;
Emma I am, since I may be no better:
But still I like it not.

THE DEVIL
Nay, come,
If ye have not everything beneath your thumb
Within the year, I have nought to say.
Haste we to Bolduc without a stay
And thenceward let us take no rest
Ere to Antwerp we have pressed;
There we shall a wonder show.
By that, the tongues ye shall wholly know
At your desire, I pledge me to ’t,
And the seven liberal arts, to boot.
Bastard and malmsey shall ye drink.
But be my friend and ye may not think
Of the marvels all ye shall do and see.—
But at last your soul belongs to me!

After these words Emma and Moonen have taken their way to
Bolduc, where for some while they tarried, feasting merrily, and
paying the shot of each and all who ate and drank in their company.
Now shall we stint a little of Emma and Moonen and tell of Sir
Gysbrecht, her eme.
After that Mary, the which now hight Emma, had been for some
while away, Sir Gysbrecht, her eme, much wondered at her tarrying,
and said with himself thus:

O anxiety, which clamors within me strong,


How dost thou rend my heart and my wit molest.
For that my niece Mary doth bide so long
Who to Nimmegen market hath her dress’d,
Where if it grew dark, I told her, as for the best,
Or haply in any wise she were frighted,
She should at my sister’s seek her rest;
There ever I lodge when I am benighted.
Nor will my troubled heart be righted
Ere I know how she doth speed.
If mischief on her hath alighted,
I die without all hope or rede,
For the lass is all I have at need,
And ever from childhood hath been my care;
If foul befall her ’twere woe indeed.
These lasses lightly fall in despair.
Now to Nimmegen I repair
To get me tidings without fail.
Men oft must hear a sorry tale.

After these words is Sir Gysbrecht gone to his sister’s house,


asking after Mary, the niece of them both, the which answered rudely
that she wist nought of her. Whereat he was right sad, saying to her
thus:

Alas, my sister, ye deceive me,


When ye say that of Mary ye nothing wot.

AUNT
Nay, good clodpate John, believe me.

UNCLE
Alas, my sister, ye deceive me.

AUNT
Nay, she is cloistered, I conceive me
Where such birds be spitted for a groat.

UNCLE
Alas, my sister, ye deceive me,
When ye say that of her ye nothing wot;
And thus with wrath yourself besot,
Though I bid you but tell in all gentleness
If ye have seen her.

AUNT
Natheless,
Say ye not her charge was mine.
She came, ’tis true, eight or ten days syne,
Saying, “Make me a bed, aunt, for to-night
I dare not go home, lest I be done despight
Of knaves who would lightly some mischief begin.”
I bade her take her once more to the inn
Where the livelong day she had sat drinking and skinking.

UNCLE
How! had she the livelong day been a-drinking?

AUNT
That you may well be thinking, and nothing loath.
And her cheeks were as red, I make an oath,
As a baby’s bottom that has been well thwack’d.
When I blamed her a little for her shameful fact,
She made as with good sharp sauce she could eat me straight.
Thus cursing and shouting she goes her gate,
And no more of my fine young lady I see.

UNCLE
Alas, what shall become of me?
O God in three, where hath she gone or far or near?

AUNT
Why, goodman dull, in the muddy wine or clear,
Where they resort as for such sport are meet.

UNCLE
Alas, my sister, ye gar me greet,
That ye make me such shameful mocks.

AUNT
Yea, had ye kept her locked up in a box,
So had your trouble not begun.
God’s son, goodman, what harm is done
If she follow her lust at large a bit?
It will not matter to her no whit
Nor fare the worse by a single straw.
She will not go halt for it.

UNCLE
This doth my spirit so adaw
I fear mine heart in four will cleave.
I must turn me about and with my sleeve
Wipe from mine eyes and cheeks a tear.

O mother of God, the which each year


In Aix I visit and adore,
Help me now as ye have done yore,
And ye in Maestricht, Saint Servace,
Devoutly have I set in place
Full many a candle, as ye wot:
I pray you now, forsake me not.

In time of need it is to one’s friends one must look;


I will now let search for her in every nook
If any of her may have heard.
Though I be stirred,
’Tis but small wonder that I grieve:
Of lief ’tis ill to take one’s leave.

After this Sir Gysbrecht departed him from his sister sad at heart
because he gat no tidings of Mary his niece.

¶ How the wicked aunt thrust a dagger in her throat.

In the meanwhile the chastelain of Grave let the old duke Arent
forth of the prison and led him to the town of Bolduc where he was
right royally received by the lords of that same. Which hearing, the
wicked aunt waxed so wrathful in her venomous heart that she well
nigh burst for spite, saying:

Help me, liver, lights, and spleen,


Teeth and head, nought goes aright!
I shall smother or split with teen:
Like a spider I swell with spite;
From my wits I be thrust out quite
At the tidings that I hear.
The old thief, in the castle that was locked tight,
He is got from Grave scot-free and clear.
Now all my comfort is but drear,
And the young duke, whom I obeyed,
Will shortly have but sorry cheer.
Such woe is me that I am near
To yield me, body and soul as I was made,
And summon all devils to mine aid.

THE DEVIL
Ha, ha! there’s profit as in this case!
Her soul is mine if I have the space
Of half an hour on her to bestow.

AUNT
Is it not noyous?

THE DEVIL
Yea, and a shrewd blow
To them as were counted the young duke’s men.

AUNT
To say the truth on’t, what is he, then,
Who ever a finer fellow saw with eye?
Yea, though in hell I must everlastingly fry,
I could cut my throat out of pure spite,
So I were done with this business quite.
Adieu and farewell, valiant young peer.
But so ye be duke in after year
Is all I ask for my shortened life.
Thus in my throat I thrust the knife
And with a blow I end me quite.
Faction has damned full many a wight.
THE DEVIL
To Hell’s convocation, in unending dole,
I summon this soul to its final fruition.
The folly of men who in factions enroll
And for some princeling get damned to perdition!
They are ours! all ours, who in this condition
Persist stubborn-hearted despite of all ill.
Envious faction gives yearly addition
To Hell of its millions, lament it who will.

¶ How Emma and Moonen journeyed to Antwerp, where they


wrought much evil.

When Emma and Moonen had for some while tarried at Bolduc
they journeyed to Antwerp whither they be speedily come. And
Moonen said unto Emma thus:

Now be we in Antwerp, as ye well would,


Here will we triumph and scatter our good.
Go we in to the “Tree” for a pint of romany.

EMMA
To the “Tree”, say ye?

MOONEN
Yes, faith, there shall ye see
All the spendthrifts that thrive by mischance;
And the wenches who know well all the old dance,
The which on ten and four hazard all at a throw.
Above sit the burghers, and the craft below,
With whom ’tis more blessed to take than to give.

EMMA
All that I would liefly behold, as I live.
Nought could be better, as to my thinking.
MOONEN
Yea, in the Gold Room we shall be drinking
Ere that we part what pleaseth you most.
Sit down, love. Yea, a first, mine host!
And if it grew musty in cask, we were evil paid.

THE DRAWER
What wine drink ye, good man?

MOONEN
A pint of grenade,
And for my wife a pint of ypocras,
And of romany a pint, the which nought doth surpass
To raise a man’s spirits when they be low.

THE DRAWER
Ay, that’s the truth. A first! ho! a first! ho!
Draw of the best and fill to the brim!

FIRST TIPPLER
See, Hans, yon is a wench that is trim.

SECOND TIPPLER
Ye say sooth, and but an ill-favored devil of a man!

FIRST TIPPLER
Let us sit by them and drink of our can.
If she be but his doxy and not his wife
We’ll filch her of him.

SECOND TIPPLER
Ay, he shall have a taste of the knife,
For he is but a foul, ill-favored lout,
But the wench is sweet flesh past all doubt.
Be she his doxy, I know where this night I shall lie.
Will aid me?

FIRST TIPPLER
In the throat, yea, that will I.
Foot to foot we will stand fast as we may.—
God a mercy, toper!

MOONEN
Pot-mates, come drink, I pray.

SECOND TIPPLER
Nay, toper, we drink of the same tun.
But may we sit you beside?

MOONEN
Yea, surely, that were well done.
Good fellowship is to me nothing loath.

FIRST TIPPLER
By your good leave, whence come ye both?

MOONEN
From Bolduc and beyond be we.

EMMA
Dear Moonen, were it not geometry
If perchance I could surely scan
How many drops of wine there be in a can?

MOONEN
Yea, love, and have ye the trick of that still?
I taught it you but yesterday.

EMMA
To forget it were ill.
Logic ye after taught me well and fair:
I hold it all fast in mind.

FIRST TIPPLER
Toper, what saith your wife there?
Can she soothly reckon to a jot
How many drops of wine be in this pot?
Of stranger thing I have never heard write.

MOONEN
She will do yet stranger in your sight.
Her like ye have never met withall;
The seven arts she hath mastered all;
Ars metric and geometry,
Logic, grammar, astronomy,
Music, and rhetoric, of ancientest repute.
With the stoutest clerk she dare dispute
In the schools of Paris or Louvain.

SECOND TIPPLER
Good toper, under your leave we were fain
See or hear some of her art.

FIRST TIPPLER
Yea, surely, and I pledge two stoups of wine for my part,
And, by cog’s ribs, if any scant her in her tale
We will shed our blood for you without fail,
In any mischief that may you befall.

MOONEN
That merry ballat, as ye may call,
Wherewith our last noonday in Highstreet ye amused,
Do ye tell o’er for these folk.

EMMA
I pray you hold me excused.
In rhetoric I be but a dull wight,
Allbe I would fain go to it with my might,
The circle of the seven arts to fulfill.
Rhetoric is not to be learned by skill;
’Tis an art that cometh of itself solely.
The other arts, if a man giveth himself thereto wholly,
These be to be learned and eke taught.
But rhetoric is to be praised beyond aught.
’Tis a gift of the Holy Ghost’s bestowing,
Though there be rude folk of such small knowing
That they reject it. ’Tis great dole
To them who love it.

SECOND TOPER
Ay, good soul,
Must we use so much argument?

FIRST TOPER
Say us somewhat, we were well content
With what ye can, and out of good will
I will eke say somewhat.

EMMA
Now, hold ye still,
For rhetoric asketh good understanding;
And after my best cunning I will sing.

O rhetoric, sweet theoric and comfortable,


I lament with dreariment that men thee hate;
Unto the heart that loves thine art ’tis lamentable.
Cry on them fy! who thee not cultivate
Or thy first finder’s fame abate!
Lewd and without shame are they.
Them I despise who do after this rate;
And to the wise ’tis grief to hear this say:

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